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US3783010A - Refracting,light permeable oxide layer and method for its manufacture - Google Patents

Refracting,light permeable oxide layer and method for its manufacture Download PDF

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Publication number
US3783010A
US3783010A US00132041A US3783010DA US3783010A US 3783010 A US3783010 A US 3783010A US 00132041 A US00132041 A US 00132041A US 3783010D A US3783010D A US 3783010DA US 3783010 A US3783010 A US 3783010A
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US
United States
Prior art keywords
layer
layers
zirconium
tantalum
light permeable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00132041A
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English (en)
Inventor
B Wille
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Balzers Patent und Beteiligungs AG
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Balzers Patent und Beteiligungs AG
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Filing date
Publication date
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Publication of US3783010A publication Critical patent/US3783010A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • C03C17/245Oxides by deposition from the vapour phase
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/083Oxides of refractory metals or yttrium
    • G02B1/105
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/23Mixtures
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/151Deposition methods from the vapour phase by vacuum evaporation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

Definitions

  • a highly retracting, light permeable oxide layer on a support comprises oxygen, zirconium and tantalum, the ratio of the number of tantalum atoms to zirconium atoms being in the range of about 1:1 to 1:2.
  • the invention relates to the production of optical layers by vacuum deposition.
  • Oxidic protecting layers serve, for example, the purpose to protect sensitive surfaces of, for example, lenses, surface mirrors and the like objects against corrosion and mechanical injury or damage.
  • Oxidic protecting layers serve, for example, the purpose to protect sensitive surfaces of, for example, lenses, surface mirrors and the like objects against corrosion and mechanical injury or damage.
  • oxidic layers are commonly used as reflection reducing coatings, interference filters, beam or ray dividers, heat filters, cold light mirrors and coatings for spectacle lenses and the like.
  • the mechanical and optical characteristics of such oxidic layers are dependent not only on the nature of the oxide which has been deposited on the respective surface, but also to a very pronounced extent on the manner in which the layer has been deposited.
  • the starting substance or substances is or are admixed with one or several rare earth elements or compounds.
  • zirconium oxide layers which, due to their high index of refraction and their nonabsorptiveness in the visible spectral region and their mechanical characteristics have been proposed for the construction of optical layer systems, unfortunately exhibit a very pronounced negative inhomogeneity. This strongly reduces, for example, the effectiveness of a reflection-reducing coating composed of such a layer.
  • Various attempts have been made to eliminate this negative inhomogeneity by changing the deposition procedure, but all these attempts have failed.
  • Some deposited layers exhibit a positive inhomogeneity.
  • Another object of the invention is to provide a method for producing a layer of this kind which is exceedingly simple to carry out with a minimum of expenditure.
  • the above objects are superiorly achieved by providing a layer on a support, which layer essentially consists of oxygen, zirconium and tantalum, the ratio of the number of tantalum atoms to zirconium atoms being in the range of 1:1 to 1:2.
  • a mixture containing the elements zirconium and tantalum in metallic or oxidic form, at least one of the elements being present in oxidic form is heated under vacuum conditions to vaporize the mixture, whereupon the vapor is condensed on the support to be coated.
  • Example 1 This test was carried out in a heatable vaporizing crucible of a vacuum deposition plant.
  • a mixture consisting of 30% of metallic tantalum, calculated on the weight of the total mixture, and 70% of zirconium oxide (ZrO were inserted into the crucible.
  • the crucible was heated with a wattage of about 2.5 kw. This resulted in a temperature of the mixture in the crucible of about 1800 C.
  • a support in the form of a glass plate was arranged in the plant opposite the crucible, and the heating resulted in vaporiza tion of the material in the crucible and the deposition of a layer of a thickness of 250 nm. with a growing speed of 35 nm. per minute.
  • the temperature of the glass plate was about 300 C.
  • the vapor deposition was carried out in known manner in an oxygen atmosphere of mm. Hg. A layer was obtained which adhered satisfactorily to the glass plate, which was hard and completely absorptionfree in the visible spectral region.
  • the constant index of refraction can be easily confirmed by proceeding in the following manner:
  • a layer to be investigated is vapor-deposited on a glass plate with a low index of refraction until, upon illumination with light of a predetermined wave length, a minimum of the reflection occurs. If the deposited layer is homogeneous, then the reflection capability of the surface of the glass plate on which the layer has been deposited, should not differ from the respective wave length from the reflection capability of the uncoated glass surface. A layer is then present which conforms to the equation wherein A indicates the respective wave length, n is the index of refraction of the layer material and d is the thickness of the layer. By contrast, a higher reflection capability relative to the uncoated glass surface is obtained if the layer is positively inhomogeneous while a lower reflection capability as compared to that of the uncoated glass surface is obtained if the layer is negatively inhomogeneous.
  • the deposition was carried out in a customary vacuum vapor deposition plant.
  • the starting mixtures were in each case heatedin a crucible to a sufficient temperature, for example, 1700 to 1800 C., so as to result in vaporization of the starting mixture.
  • the manner of heating the mixture in the crucible is not critical and can be efiected by known ways, for example, a tungsten crucible may be used which is heated by electric resistance heating, or the heating is effected by means of an electron beam. In the latter case, the electron beam is directed onto the surface of the mixture to be vaporized which thus is directly heated to the evaporation temperature.
  • the heat efiect of the electron beam is, as is known, the product of the current intensity of the beam and the applied potential.
  • layers were obtained which are completely homogeneous in the above indicated sense, although the deposition was carried out with a growth rate of the layers on the support of about 350 A per minute up to layer thicknesses of about 300 nm.
  • the layers obtained in accordance with the invention may be used for numerous purposes. For example, they are extremely suitable, as already mentioned, for the build-up of multi-layer coatings. Such multi-layer coatings, as compared to single-layer reflection-reducing coatings have the advantage that they result in a significantly stronger reduction of the reflection of a coated surface.
  • the tantalum-suboxide mentioned in Table 2 may be obtained by melting together a stoichiometric mixture of tantalum metal and tantalum-pentoxide while the mentioned zirconium-suboxide may be obtained by melting together a stoichiometric mixture of zirconium metal and zirconium-dioxide.
  • the melting-together may be effected in advance of the vapor deposition in a preceding step to obtain the respective suboxide, or it may be effected in the vaporizing crucible proper in which event the starting mixture contains three components.
  • the crucible would be fed with a mixture of metallic tantalum, Ta O and ZrO while, in respect to Example 7, the mixture in the crucible would consist of Ta O Zr and ZrO
  • the inventive procedure results in the formation of layers of predetermined composition, to wit, the layer consists of oxygen, tantalum and zirconium. It is assumed that in the ideal case, the ratio of the number of atoms of tantalum to the number of atoms of zirconium is about 1:1.5. For practical requirements, however, it is not necessary to adhere to this theoretical value, but values deviating therefrom also give excellent results.
  • the measurement of the ratio is subject to measuring errors.
  • the atomic ratio in the inventive layer is always within a limit range and that the ratio of the number of tantalum atoms to the number of zirconium atoms is thus always between 1:1 to 1:2.
  • investigations by X-ray diagrams have indicated that the inventive layers do not contain any crystalline zirconium oxide, or if crystalline zirconium oxide is contained in them, the amount is extremely small. This explains the superior homogeneity of the inventive layers.
  • inventive layers may be successfully employed for interference systems with satisfactory ultraviolet permeability. This is so because the layers up to a value of about 340 nm. may be produced without exhibiting any absorption whatsoever.
  • the single figure shows a support having an inventive layer deposited thereon.
  • the support in the form of a glass plate, has deposited thereon the layer 2 consisting of tantalum, zirconium and oxygen.
  • the layer is light permeable and highly retracting, and essentially consists of oxygen, zirconium and tantalum, the ratio of the number of tantalum atoms to zirconium atoms in the layer being in the range of 1:136 to 1:1.7, said layer being essentially devoid of crystalline zirconium oxide.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physical Vapour Deposition (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Surface Treatment Of Glass (AREA)
US00132041A 1970-04-13 1971-04-07 Refracting,light permeable oxide layer and method for its manufacture Expired - Lifetime US3783010A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH549170A CH527916A (de) 1970-04-13 1970-04-13 Verfahren zur Herstellung einer hochbrechenden lichtdurchlässigen Oxidschicht

Publications (1)

Publication Number Publication Date
US3783010A true US3783010A (en) 1974-01-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
US00132041A Expired - Lifetime US3783010A (en) 1970-04-13 1971-04-07 Refracting,light permeable oxide layer and method for its manufacture

Country Status (9)

Country Link
US (1) US3783010A (de)
JP (1) JPS5430997B1 (de)
AT (1) AT305515B (de)
CH (1) CH527916A (de)
DE (1) DE2050556C3 (de)
FR (1) FR2086008B1 (de)
GB (1) GB1328298A (de)
NL (1) NL142459B (de)
SE (1) SE358143B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900609A (en) * 1970-04-13 1975-08-19 Balzers Patent Beteilig Ag Method for manufacture of a refracting, light permeable oxide layer
US4260222A (en) * 1978-07-11 1981-04-07 Olympus Optical Co., Ltd. Multi-layer non-reflecting film
WO2004067463A1 (en) * 2003-01-28 2004-08-12 Philips Intellectual Property & Standards Gmbh Transparent zirconium oxide - tantalum and/or tantalum oxide coating

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3009533C2 (de) * 1980-03-12 1986-11-06 D. Swarovski & Co., Wattens, Tirol Belag mit mittlerem Brechwert, Verfahren zu dessen Herstellung und Verwendung des Belages
DE3026703C2 (de) * 1980-07-15 1983-01-27 Will Wetzlar Gmbh, 6330 Wetzlar Verfahren zur Herstellung eines Antireflexbelages auf einem transparenten Material, wie einem optischen Glas
JPS5931147A (ja) * 1982-08-17 1984-02-20 株式会社豊田中央研究所 可視光透過性熱線しやへい膜およびその製造方法
JP6645012B2 (ja) * 2015-01-29 2020-02-12 日亜化学工業株式会社 蒸着材料

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900609A (en) * 1970-04-13 1975-08-19 Balzers Patent Beteilig Ag Method for manufacture of a refracting, light permeable oxide layer
US4260222A (en) * 1978-07-11 1981-04-07 Olympus Optical Co., Ltd. Multi-layer non-reflecting film
WO2004067463A1 (en) * 2003-01-28 2004-08-12 Philips Intellectual Property & Standards Gmbh Transparent zirconium oxide - tantalum and/or tantalum oxide coating
US20060280950A1 (en) * 2003-01-28 2006-12-14 Arnd Ritz Transparent zirconium oxide-tantalum and/or tantalum oxide coating
US7521871B2 (en) 2003-01-28 2009-04-21 Koninklijke Philips Electronics, N.V. Transparent zirconium oxide-tantalum and/or tantalum oxide coating

Also Published As

Publication number Publication date
NL7008641A (de) 1971-10-15
NL142459B (nl) 1974-06-17
CH527916A (de) 1972-09-15
GB1328298A (en) 1973-08-30
AT305515B (de) 1973-02-26
DE2050556B2 (de) 1973-06-20
DE2050556C3 (de) 1978-11-30
JPS5430997B1 (de) 1979-10-04
SE358143B (de) 1973-07-23
FR2086008A1 (de) 1971-12-31
DE2050556A1 (de) 1971-12-02
FR2086008B1 (de) 1975-06-06

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